CA1247143A - Methane conversion - Google Patents
Methane conversionInfo
- Publication number
- CA1247143A CA1247143A CA000507766A CA507766A CA1247143A CA 1247143 A CA1247143 A CA 1247143A CA 000507766 A CA000507766 A CA 000507766A CA 507766 A CA507766 A CA 507766A CA 1247143 A CA1247143 A CA 1247143A
- Authority
- CA
- Canada
- Prior art keywords
- contact material
- methane
- accordance
- conversion
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 claims abstract description 115
- 238000000034 method Methods 0.000 claims abstract description 62
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 46
- 239000001301 oxygen Substances 0.000 claims abstract description 46
- 239000007789 gas Substances 0.000 claims abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 35
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 230000001590 oxidative effect Effects 0.000 claims abstract description 24
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052738 indium Inorganic materials 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- 239000010955 niobium Substances 0.000 claims abstract description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003345 natural gas Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 23
- 150000002367 halogens Chemical class 0.000 claims description 23
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 37
- 239000005977 Ethylene Substances 0.000 abstract description 37
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract description 26
- -1 natural gas Chemical compound 0.000 abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- HWSISDHAHRVNMT-UHFFFAOYSA-N Bismuth subnitrate Chemical compound O[NH+]([O-])O[Bi](O[N+]([O-])=O)O[N+]([O-])=O HWSISDHAHRVNMT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 241000193803 Therea Species 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229960001482 bismuth subnitrate Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006902 nitrogenation reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 1
- 235000018341 sodium sesquicarbonate Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- C—CHEMISTRY; METALLURGY
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Abstract
Abstract of the Disclosure A method for the oxidative conversion of a feed material comprising methane, such as natural gas, to higher hydrocarbons, particularly ethylene and ethane and desirably ethylene, in which feed is contacted with a solid contact material comprising cobalt; at least one metal selected from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth, preferably, zirconium; phosphorous; at least one Group IA metal; and oxygen under oxidative conversion conditions sufficient to convert the methane to the higher hydrocarbons. Substantial improvement in the conversion of methane and selectivity to ethylene and ethane is obtained by adding chlorine to the contact material. The further addition of sulfur to the contact material also improves the conversion and selectivity and permits the method to be carried out in an essentially continuous manner in the presence of a free oxygen containing gas.
Description
PATENT
~ 3 31754CA
MET~E CONVERSION
The present invention relates to methane conversion. In a more specific aspect, the present invention relates to me-thane conversion -to higher hydrocarbons. In a still more specific aspect, the pxesent invention relates to methane conversion to ethylene and ethane.
Background of the Invention 0lefins, such as ethylene and propylene, have become major feedstocks in the organic chemical and petrochemical industries. 0f these, ethylene is by far the more important chemical feedstock, since the requirements for ethylene feedstocks are about double those for propylene feedstocks. Consequently, feedstocks for the production of ethylene are in relatively short supply.
Numerous suggestions have been made for the production of ethylene from various feedstocks by a varie-ty of processes.
At the present time, ethylene is produced almost exclusively by dehydrogenation or pyrolysis of ethane and propane, naptha and, in some instances, gas oils. About 75% of the ethylene is produced by steam cracking of ethane and propane derived from natural gas. However, natural gas contains as little as 5 volume percent and, in rare instances, as much as 60 volume percent of hydrocarbons o-ther than methane, the majority of which is ethane. However, typical natural gases contain less than about 12 to 15% of ethane. In addition to the rela-tively small quantities of ethane and propane available for use, separation of these components from natural gas is itsel~ an expensive and complex process, usually involving compression and expansion, cryogenic techniques and combinations thereof.
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~4~ '~
:~,i;;". -~ ~d~ ~IL ~ 31754CA
It would, therefore, be highly desirable to be able to produce ethylene Erom the much more abundant methane. However, methane's high molecular stability, compared to other aliphatics, makes its use in ethylene product:ion difficult and no significant amount of ethylene is produced commercially from methane at the present time.
Pyrolytic or dehydrogenative conversion of methane or natural gas to higher hydrocarbons has been proposed. However, relatively severe conditions, particularly temperatures in excess of 1000C, are required.
In addition, such reactions are highly endothermic and ~hus energy intensive. In order to reduce the severity of the conditions, particularly temperature, numerous proposals to catalyze pyrolytic reactions have been made. Some of th~se processes do, in fact, reduce the required temperatures, but the conversion of methane and the selectivity to ethylene are still quite low.
Another promising approach is the oxidative conversion of methane or natural gas to higher hydrocarbons. However, these techniques are still in the developmental stage and experimentation is hampered by differences of opinion and lack of a complete 1mderstanding of the process. For example, most workers in the art refer to the process as "oxidative coupling". However, there is little agreement with regard to the function performed by the oxygen and how this function is performed.
Accordingly, the terminology, "oxidative coupling", will be avoided herein, and the present process, irrespective of the function of the oxygen or of the manner in which it performs its function, will be referred to as "oxidative conversion of methane". In such processes, it is conventional to contact the methane with solid materials. The nature of these contact materi.als, the function thereof and the manner in which such function is performed are also subject to diverse theories. ~or example, workers in the art refer to the function of the contact ma-terial as a purely physical phenomenon, in some cases as adsorption-desorption either of atomic or molecular oxygen and either on the surface or occluded within the solid material, oxidation-reduction utilizing multivalent metals capable of oxidation-reduction, adsorption and desorption of the hydrocarbons on the solid materials, a free radical mechanism, etc. Consequently, the solid materials, utilized in the process, are referred to as "contact materials", "promoters", ~ ~ 7~ 3175~CA
"activators" and "catalysts". According:Ly, in order to avoid Eunctional categorization, the terms "solid contact material" or "sol:id contact materials" will be utilized in -the present application.
Based on the prior art, oxidative conversion of methane reswlts in the formation of a variety of products. The most readily produced products are carbon dioxide, carbon monoxide and/or water and methanol, formaldehyde and other oxygenated hydrocarbons in combina-tion with one or more oE carbon dioxide, carbon monoxide and water. Higher hydrocarbons, par-ticularly ethylene and ethane~ are either not formed or are formed in such small quantitites that commercially viable processes have not been developed to date. Along with poor selectivity to higher hydrocarbons, particularly ethylene and ethane and still more particularly to ethylene, such processes also result in low conversions of the methane feed.
It is clear from the above that the suitability of particular contact materials is unpredictable. In addition to being dependent upon the type of contact material, the conversion of methane and selectivity to particular products also depends upon the conditions and the manner in which the reaction i9 -arried out, and -~here is also little basis for predicting what conditions or what mode of operation will result in high0 conversions and selectivity to particular products.
Summary of the Invention It is therefore, an object of the present invention to provide an improved method for the conversion of methane. Another and further object is to provide an improved method for the oxidative conversion of methane. Yet another object is to provide a method for the oxidative conversion of methane at improved conversion levels. Another and further object of the present invention is to provide a method for the oxidative conversion of methane, which results in improved selectivity -to higher hydrocarbons. A further object of the present invention is to provide a method for the oxidative conversion o~ methane, which results in improved conversion and selectivity to higher hydrocarbons. A still further object of the present invention is to provide a method for the oxidative conversion of methane, which results in improved selectivity to ethylene and ethane. Yet another object of the present invention is to provide a methcd for the oxidative conversion of methane, which results in improved conversion and selectivity to ethylene and ethane. Another object of the ~7~3 31754CA
present invention is to provide a method Eor the oxidative conversion of methane, which results in improved selectivity to ethylene. Another and further object of the present invention i8 to provide a method .Eor the oxidative conversion of methane, which results in improved corlversion and selectivity to ethylene. A further object oE the present invention is to provide a method for the oxidative conversion of methane, which can be carried out utiliæing inexpensive starting materials. Another object of the present invention is to provide a method for the oxidative conversion of methane, which can be carried out under relatively mild conditions. A
still further object of the presen-t invention is to provide a method for the oxidative conversion of methane utilizing an improved contact material.
These and other objects and advantages of the present invention will be apparent from the following description.
In accordance with the present invention it has been found that methane can be converted to higher hydrocarbons, particularly ethylene and ethane, by:
contacting a feed material comprising methane with a solid contact material, comprising:
cobalt; at least one metal selected from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth; phosphorous; at least Group IA metal; oxygen, and, optionally, a material selected from the group consisting of a halogen and sulfurj under oxidative conversion conditions sufficient to convert said methane to said higher hydrocarbons.
Substantially improved conversion of methane and selectivity to higher hydrocarbons, particularly ethylene and ethane, is obtained by the addition of a halogen, preferably chlorine.
The method can be carried out in a cyclic manner (methane conversion, preferably followed by a purge with an inert gas, such as nitrogen, and regeneration by contact with a free oxygen containing gas).
However, the further addition of sulfur to the contact material not only increases conversion of methane and selectivity to higher hydrocarbons, particularly ethylene and ethane, but permits the method to be carried out in a continuous manner (by contacting a methane-containing gas and a free oxygen containing gas with the contac-t material).
7~3 3l75l~CA
Zirconium is a preferred metal from the group consisting of æirconium, zinc, niobium, indium, lead and bismuth. The preferred Group IA metal is sodiwm. However, the addition of a second Group I~ metal, preferably potassium, improves results ~Inder certain operating conditions.
Detailed De~ ption In accordance with the present inven-tion~ it has been found that substantially improved conversion of methane to higher hydrocarbons can be obtained by the oxidative conversion of methane to produce higher hydrocarbons at substantially improved selectivities, particularly to ethylene and ethane, by:
contacting a methane-containg gas with a solid contact material, comprising:
cobalt; at least one metal selected from the group consisting of zirconium, ~inc, niobium, indium, lead and bismuth; phosphorous; at least one Group IA metal; oxygen, and, optionally, at least one material selec-ted from the group consisting of a halogen and sulfur, under oxidative conversion conditions suEficient to convert the methane to higher hydrocarbons, particularly ethylene and ethane.
A preferred metal from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth is zirconium. A preferred Group IA
metal is sodium, resulting in the following combination:
Co/Zr/P/Na/0 While the above contact material is capable of converting methane to higher hydrocarbons, particularly ethylene and ethane, the conversion and selectivity are relatively poor. ~lowever, the addition oi a halogen, such as chlorine, to this composition substantially improves both the conversion of methane and the selectivity to higher hydrocarbons, particularly ethylene and ethane. The chlorine can be added to the contact material during its preparation, thus resul-ting in the following contact material:
Co/Zr/P/Na/Cl/0 or by pretreating the contact material with a halogen-containing gas în the reac-tor prior to conduct of -the reaction, as will be detailed hereinafter in the description of the preparation of the contact material and the methods of operation.
~ 3 31754CA
In accordance with most previous theories of the function and operation of contact materials for the oxidative conversion of methane to higher hydrocarbons, particularly ethylene and ethane, the reaction has been carried out in the absence of a Eree o~ygen containing gas, with the oxygen theoretically being supplied by the contact material. As a result, the most utilized modes of operation have included treating the contact material wi-th a free oxygen containing gas, such as oxygen or air, for a period of time sufficient to produce a reducible oxide of a multivalent metal, thereafter, contacting methane wi-th the reducib:le metal oxide and, thereafter, treating the reduced metal oxide with a free oxygen containing gas to "regenerate" the same. Similarly, certain contact materials are contacted with a free oxygen containing gas to cause adsorption of oxygen on the contact material, methane is, thereafter, contacted with the contact material containing adsorbed oxygen and, thereafter, the contact material is again treated with a free oxygen containing gas. In both instances, the contact material, after treatment with a free oxygen containing gas, is purged with an inert gas, such as nitrogen, to remove excess oxygen which has not reacted with or been adsorbed on the contact material. Consequently, several techniques have been followed, including, carrying out the contact with methane and the con-tact wi-th a free oxygen containing gas in separate reaction chambers or sequentially passing a free oxygen containing gas, a purge gas and methane through the contact material in a single reaction vessel.
The disadvantages of either of these procedures will be evident to one skilled in the art.
The method of the present invention can be carried out in a cyclic manner as set for-th above. For example, the methane feed can be passed through a fixed bed of the contact material ~mtil such time as the conversion and/or selectivity reach an unacceptable point. Flow of feed methane is then discontinued and the catalyst is purged with an inert gas, such as nitrogen. Following this purge, a free oxygen containing gas, such as air, is passed therethrough to regenerate the contact material. This cycle is then repeated. Some of the problems with such a cyclic operation are pointed out above and these and others are well known to those skilled in the art.
3~754C~
It has been Eound that the me-thod can be carried out in an essentially continuous manner while at the same time further increasing both the conversion of methane and the selectivity to higher hydrocarbons, particularly ethylene and ethane, by the further addition of sulfur to the contact material. This will result in the following contact material:
Co/Zr/S/P/Na/Cl/0 A brief example of such an operation involves passing a methane-containing gas and a free oxygen containing gas over the above mentioned contact material. When utili~ing this contact material and carrying out the method in an essentially continuous manner, it has been found that the contact material maintains its conversion and selectivity abilities for extended periods of time without further treatment of the contact material or regeneration. However, should such further treatment or regeneration be necessary or desirable, this contact material can also be treated or regenerated periodically as detailed hereinafter.
While -the preferred alkali metal is sodium, as set forth above, it is also desirable to include a second Group IA metal, particularly potassium, thereby resulting in the following contact material:
Co/Zr/S/P/Na/K/Cl/0 The inclusion of potassium in the contact ma-terial has some effect on the conversion of methane and selectivity to higher hydrocarbons but can be eliminated. ~owever, the presence or absence of potassium is significant if a particular method of forming the contact material and operating the process is followed. Specifically, if a halogen, particularly chlorine, is included in the catalyst, which of course is necessary for best results, the presence or absence of potassium is not a significant ~factor. However, if -the contact material is prepared without the halogen, the halogen may be added by pretreating the contact material with a halogen-containing gas, such as methyl chloride, and, thereafter, passing the feed over the contact material for the reaction. In -this case, the presence or absence of potassium is not too significant.
However, if the contact material is prepared without the halogen and a gas containing halogen is co-fed with the feed material, during the reaction, in an effor-t to supply the halogen, then the presence of potassium in the contact material appears necessary.
~ 7~3 31754CA
In addition to methane, the hydrocarbon Eeedstock, employed in the me~hod o-f the present invention, may contain other hydrocarbon or non-hydrocarbon components. The presence of ethane, propane and the like is not detrimen-tal. It has been found that carbon dioxide and water are not detrimen-tal, since they are often products of the process. It has also been found that inert gases, such as nitrogen, helium and the like are not detrimental. Consequently, the method of the present invention can effectively utilize any conventional na-tural gas.
The free oxygen containing gas may be any sui-table oxygen containing gas, such as oxygen, oxygen-enriched air or air. The method of the present application has been effec-tively carried out utilizing air as a source of oxygen.
When utilized in -the present invention, the term "diluent gas"
is meant to include any gaseous material, present in the methane-containing gas, the free oxygen containing gas or in the form of an added gas, which is essentially inert with respect to the oxidative conversion of methane and, thus, does not significantly decrease the conversion of methane and/or the selectivity to the production of higher hydrocarbons.
As previously pointed out, cer-tain of the components of the contact material are an absolute necessity (cobalt, a metal selected from the ~roup consisting of zirconium, æinc, niobium, indium, lead and bismuth, phosphorous, at least one Group IA metal and oxygen). A halogen is necessary in order to attain acceptable conversion and selectivity.
T~e sulfur is necessary to permit essentially continuous operation o-f the method. A second Group IA metal, such ~s potassium, is desirable.
However, the rela~ive proportions of the components does not appear to be particularly critical. Accordingly, any amounts of the individual components may be present so long as effective amounts of the other components are present. The term "effective amount" is used herein to identify the quantity of the component which, when present in the contact material, results in a significant inerease in the conversion of methane and/or the selectivity to higher hydrocarbons, particularly ethylene and ethane, compared with a contact material without the component in question. Preferably, however, the cobalt and the metal selected from the group consisting of zirconium, zinc, niobium, indium, lead and 3175~1C~
bismuth are utilized as major components whi:Le tke remaining components are utilized in minor amounts. By way of example, the preferable atorllic ratio of cobalt to the metal selected Erom the group consisting of zirconium, zinc, niobium, indium, lead and bismuth is in the range of about 1/1 to about 20/1 and more preferably in the range of abou-t 3/1 to about 6/l. The phosphorous is preferably present in an amount of about 1 w-t. percent to about 10 wt. percent and more preferably between about 2 wt. percent and about 5 wt. percen-t, expressed in terms of phosphorous oxide based on the total weight of the contact material. Preferably, the alkali metal is present in concentrations of about 1 wt. percent to about 10 wt. percent and more preferably between about 2 wt. percent and about 5 wt. percent, also expressed in terms of alkali metal oxide based on the total weight of the contact material. Preferred concentrations of sulfur are in the range of about 1 wt. percent to about 10 wt. percent and more preferably between about 2 wt. percent and about 5 wt. percent, expressed in terms of elemental sulfur based on the total weight of -the contact material. The halogen is preferably present in an amount between about 1 wt. percent and about 10 wt. percent and more preferably between about 2 wt. percent and about 5 wt. percent, expressed in terms of elemental halogen based on the total weight of the contact material.
In addition to the appropriate composition, the method of preparation of the contact material is a critical factor in order to obtain an acceptable catalyst, i.e., active, selective and relatively long lived. While it is not intended to restrict the presen-t invention to any particular ~orm of the components or mode of operation in the reaction, it is believed that the contact material is a complex mixture of oxides of the elements contained therein, with the possible e~ception that sulfur and chlorine, which may be present in sulfides or chlorides, thus reducing the amount of oxygen needed to stoichiometrically balance the remainder of the components therein. Theoretically, it is also believed that the components should be in their lower states of oxidation and that some minimal concentration of halogen is necessary.
The contact materials can be prepared by any suitable me-thod known in the art for the preparation of such mixtures in a solid form.
Conventional methods include co-precipitation from an aqueous, an organic or a combination solution-dispersions, impregnation, dry mixing, wet ~ ~r~ 3 31754CA
''` 10 mixing or the like, alone or in various combinations. In general any method can be used which provides contact materials containing the prescribed components in eE~ective amounts. The contact material can be prepared by mixing the ingredients in a blender with enough water to form a thick slurry. The slurry can then be dried, usually the temperat-lre sufficient to volatalize the water or other carrier, such as about 220F
to about 450F and, thereafter, calcined, for example, at about 700F to about 1200F for from 1 to 24 hours. It is believed that the drying step, previously mentioned, results in at least some of -the components being in a higher state of oxidation and, therefore, resulting in an unacceptable contact material. Consequently, it is believed that the components must be reduced -to lower states of oxidation to produce an acceptable contact material. This can be accomplished in several ways.
In accordance with one mode of operation, the contact material is calcined in an oxygen ree atmosphere, for example, in the presence of an inert gas, such as ni-trogen, or a reducing gas, such as hydrogen, methane, ethane, etc. The mode of contacting with the oxygen free atmosphere is also believed significant. For example, it has been found that calcining the contact ma-terial in an open dish while blowing nitrogen through the furnace results in an unacceptable contact material.
On the other hand, when the contact material was calcined in a closed container with nitrogen moving through the solid mass, an acceptable catalyst was obtained. Obviously, the contact material could be calcined in a vacuum but this is impractical. As an alternative, the simpler procedure of calcining in air can be carried out and the contact material placed in the reactor and pretreated with a reducing gas, such as the methane feed, in the absence of oxygen. ~ollowing the pretreatment, the methane eed and oxygen are passed through the reactor to carry out the reaction. The contact material can also be initially prepared without the halogen and, therea~ter, the halogen can be supplied by pretreating the contact material in the reactor with a halogen-containing gas such as methyl chloride, me-thylene chloride, etc. Obviously, if the contact material is prepared by calcining in air and without halogen, the pretreatment would co~prise treatment wi-th a halogen containing gas and a reducing gas in either sequence or in combination. While work to date has not shown any significant deactivation of the contact material during ~ 3 3l754CA
the reaction, either with respect to the conversion oE methane or the selectivity to higher hydrocarbons, it may, from time to time, be necessary to regenerate -the contact material. As previously pointed out, a certain minimal level of chlorine on or near the surface of the contact material appears necessary and it also appears that the contact material should be in a lower state of oxidation. During use for some purposes, it has been found that the contact material deteriorates to some exten-t by loss of chlorine and overoxidation. To the extent that these phenomena occur, it has been found that the contact material may be reactivated or regenerated by stopping the flow of feed methane and free oxygen containing gas, passing a halogen containing gas through the contact material and, thereafter, passing a reducing gas, such as the feed methane alone, through the contact material. This treatment returns the activity and selectivity of the contact material to essentially its original condition.
Any suitable cobalt compound may be utilized in preparation of the contact material. For example, such compounds would include cobalt acetate, cobalt carbonate, cobalt nitrate, cobalt oxides and cobalt halides. Preferably, the cobalt is present in the preparation material as cobalt sulfide. However, other sulfur compounds may be used such as zirconium, cobalt, sodium, potassium, ammonium sal-ts of sulfur, thiocyanide or thiosulfate.
Any suitable compounds of the metal selected from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth may also be utili~ed in the preparation. Zinc compounds could include zinc acetate, zinc halides, zinc nitrate, zinc carbonate and zinc oxide.
Titanium compounds can include titanium tetrachloride and titanium dioxide. Suitable zirconium compounds include zirconium tetrachloride, zirconyl nitrate, zirconyl acetate and zirconium dioxide. Niobium compounds include niobium chloride and niobium oxide. Suitable indium compounds can be utilized, such as indium chloride, indium hydroxideS
indium nitrate, indium acetate and indium oxide. Lead compounds which may be utilized include lead chloride, lead nitrate, lead acetate, lead carbonate and lead oxides. Bismuth may be in the form of bismuth trichloride, bismuth nitrate, bismuth subnitrate and bismu-th trioxide.
~ 3 3175~CA
lZ
The alkali metal and phosphorous are preferably added to the preparation composition as sodium dihydrogenorthophosphate, disodiummonohydrogenorthophosphate, trisodiumorthophosphate and sodiumpyrophosphate. The alkali metal and phosphorous can be incorporated separately, utilizing sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium nitrate and sodium acetate and ammonium hydrogen phosphates. As previously indicated, it is believed that -the contact material is a complex mixture of oxides.
Consequently, it is preferred that -the starting materials be in -their oxide form or in -the form of compounds which, upon drying and/or calcining, are converted to oxides.
In the present invention, it has been found -that the method can be carried out between two extremes, namely, low conversion of methane/high selectivity to higher hydrocarbons, particularly ethylene, and high conversion of methane/low selectivity to the higher carbons, particularly ethylene. The process parameters (space velocity, temperature, and reactant partial pressure) can, to some extent, be used to control the reaction at the desired point between these two limits.
Consequently, the reaction conditions may vary between broad limits.
The vol~etric ratio of methane to free oxygen should be in excess of about 1/1, preferably it is between about 1/1 and about 30/1 and still more preferably between about 4/1 and about 15/1. It has been found that a ratio of methane to free oxygen of at least about 1/1 is necessary, in accordance with the present invention, in order to obtain maximum conversion of methane and high selectivity to higher hydrocarbons, particularly ethylene.
The temperature is preferably at least about 500C and will generally vary between about 500C and about 1500C. However, in order to obtain high conversions of methane and high selectivities to ethylene and ethane, the temperature is preferably between about 500C and about 900C and most desirably between about 600C and about 800C.
It has also been found that, as the partial pressure of oxygen is increased, the selectivity to higher hydrocarbons decreases and the selectivity to carbon dioxide increases and vice versa. Total pressures may vary anywhere from around 1 atmosphere to about 1500 psi but are preferably below about 300 psi and ideally below abou-t 100 psi.
~ 31754C~
nethane f]ow rates can also vary over a wide range, for example, from 0.5 to 100 cubic centimeters per mi.nute per cubic centimeter of contact ma-terial. Preferably, however, the rate is between about 1.0 and about 75 c-Lbic centimeters per minute per cubic centimeter of contact material.
The total flow velocities of all gaseous materials, including diluents, through a fixed bed reactor, may be at any rate effective for the oxidative conversion reaction. For example from 50 to 10,000 GHSV
and preferably from 500 to 5000 GHSV.
In addition to the high conversion oE methane and high selectivity to ethylene and ethane, attainable in accordance with the present invention, the contact materials are not readily poisoned and will tolerate the presence of water, carbon dioxide, carbon monoxide and the like. In addition, the contact materials appear to be long lived, with no noticeable deactivation problems. Concomitantly, the process can be carried out sontinuously in fixed, moving, fluidized, ebullating or entrained bed reactors.
The following examples illustrate the nature and advantages of the present invention.
In the runs of the examples, the contact materials were prepared by aqueous slurrying, drying and calcination.
The contact material was loaded in a quartz reactor having a thermocouple well centered in the contact material bed. The reactor was brought up to temperature under ni-trogen or air and, thereafter, methane and air flow was begun. The gas inlet system included electronic flow measurement, a three-~one furnace for heating reactant gases and the contact material and a downstream analysis system. The reactor effl~ent was snap sampled, at any desired time, and analyzed for all paraffins and olefins between Cl and C4 and N2, 2, C0 and C02, by gas chromatography.
All contact materials are referred to in terms of weight percent of the designated element, based on the total weight of contact material.
The variables and results of this series of tests are set forth in the Table below. Conversion is mole percent of methane converted.
Selectivity and yields are based on mole percen-t of methane feed converted to a particular product. The CH~ rate can be expressed as cc/min/cc of contact material. ~or example, when 70 cc/min of CH~ was ~ 7~3 31754CA
fed to a reactor containing 20 cc of catalyst the flow ra-te would be 3.5 cc/min of CH~/cc of contact material. The volumetric ratio of CH4 to oxygen is also parenthetically given in terms of cc/min of Cll~ per cc/min of other gases (air) present. The Co/Zr/S/P/Na/K/Cl/0 contact mater:ial was prepared by the following procedure: 107.1 g of CoCl2 was dissolved in 250 m~ of distilled water and 118.9 g of Na2S was dissolved in 250 ml of water. These two solutions were combined and stirred for about 20 minutes, filtered, using a Buchner funnel, the precipitate was washed in distilled water and refiltered. An aqueous slurry of the resultant CoS
was formed with Na4P207 10H20(7.5g)Na, X0~1(1.5g), ~rO(N03)2 nH20(26.7g) and NH4C1(5.4g). The slurry was then dried over night in a forced draft oven. The dried contact ma-terial was calcined in a quartz calcining reactor for three hours at 1500F in a flowing nitrogen atmosphere. The calcined contact material was then ground and sieved to 20/40 mesh.
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- l6 It has also been found that the production of CO2 was high and, hence, the HC selectivi-ty was low, if the concentration o~ 2 in the initial feed stream is high. Accordingly, the ~IC selectivity can be increased and the CO2 production concom:ittantly decreased by staged addition oE the free oxygen containing gas to provide an effective portion of the total 2 at a plurality of spaced points along a continuous contact material bed or between separate con-tact material beds.
While specific materials, conditions of operation, modes of operation and equipment have been reierred to herein, it is to be recognized that these and other specific recitals are for illustrative purposes and to set forth the best mode only and are not to be considered limiting.
~ 3 31754CA
MET~E CONVERSION
The present invention relates to methane conversion. In a more specific aspect, the present invention relates to me-thane conversion -to higher hydrocarbons. In a still more specific aspect, the pxesent invention relates to methane conversion to ethylene and ethane.
Background of the Invention 0lefins, such as ethylene and propylene, have become major feedstocks in the organic chemical and petrochemical industries. 0f these, ethylene is by far the more important chemical feedstock, since the requirements for ethylene feedstocks are about double those for propylene feedstocks. Consequently, feedstocks for the production of ethylene are in relatively short supply.
Numerous suggestions have been made for the production of ethylene from various feedstocks by a varie-ty of processes.
At the present time, ethylene is produced almost exclusively by dehydrogenation or pyrolysis of ethane and propane, naptha and, in some instances, gas oils. About 75% of the ethylene is produced by steam cracking of ethane and propane derived from natural gas. However, natural gas contains as little as 5 volume percent and, in rare instances, as much as 60 volume percent of hydrocarbons o-ther than methane, the majority of which is ethane. However, typical natural gases contain less than about 12 to 15% of ethane. In addition to the rela-tively small quantities of ethane and propane available for use, separation of these components from natural gas is itsel~ an expensive and complex process, usually involving compression and expansion, cryogenic techniques and combinations thereof.
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It would, therefore, be highly desirable to be able to produce ethylene Erom the much more abundant methane. However, methane's high molecular stability, compared to other aliphatics, makes its use in ethylene product:ion difficult and no significant amount of ethylene is produced commercially from methane at the present time.
Pyrolytic or dehydrogenative conversion of methane or natural gas to higher hydrocarbons has been proposed. However, relatively severe conditions, particularly temperatures in excess of 1000C, are required.
In addition, such reactions are highly endothermic and ~hus energy intensive. In order to reduce the severity of the conditions, particularly temperature, numerous proposals to catalyze pyrolytic reactions have been made. Some of th~se processes do, in fact, reduce the required temperatures, but the conversion of methane and the selectivity to ethylene are still quite low.
Another promising approach is the oxidative conversion of methane or natural gas to higher hydrocarbons. However, these techniques are still in the developmental stage and experimentation is hampered by differences of opinion and lack of a complete 1mderstanding of the process. For example, most workers in the art refer to the process as "oxidative coupling". However, there is little agreement with regard to the function performed by the oxygen and how this function is performed.
Accordingly, the terminology, "oxidative coupling", will be avoided herein, and the present process, irrespective of the function of the oxygen or of the manner in which it performs its function, will be referred to as "oxidative conversion of methane". In such processes, it is conventional to contact the methane with solid materials. The nature of these contact materi.als, the function thereof and the manner in which such function is performed are also subject to diverse theories. ~or example, workers in the art refer to the function of the contact ma-terial as a purely physical phenomenon, in some cases as adsorption-desorption either of atomic or molecular oxygen and either on the surface or occluded within the solid material, oxidation-reduction utilizing multivalent metals capable of oxidation-reduction, adsorption and desorption of the hydrocarbons on the solid materials, a free radical mechanism, etc. Consequently, the solid materials, utilized in the process, are referred to as "contact materials", "promoters", ~ ~ 7~ 3175~CA
"activators" and "catalysts". According:Ly, in order to avoid Eunctional categorization, the terms "solid contact material" or "sol:id contact materials" will be utilized in -the present application.
Based on the prior art, oxidative conversion of methane reswlts in the formation of a variety of products. The most readily produced products are carbon dioxide, carbon monoxide and/or water and methanol, formaldehyde and other oxygenated hydrocarbons in combina-tion with one or more oE carbon dioxide, carbon monoxide and water. Higher hydrocarbons, par-ticularly ethylene and ethane~ are either not formed or are formed in such small quantitites that commercially viable processes have not been developed to date. Along with poor selectivity to higher hydrocarbons, particularly ethylene and ethane and still more particularly to ethylene, such processes also result in low conversions of the methane feed.
It is clear from the above that the suitability of particular contact materials is unpredictable. In addition to being dependent upon the type of contact material, the conversion of methane and selectivity to particular products also depends upon the conditions and the manner in which the reaction i9 -arried out, and -~here is also little basis for predicting what conditions or what mode of operation will result in high0 conversions and selectivity to particular products.
Summary of the Invention It is therefore, an object of the present invention to provide an improved method for the conversion of methane. Another and further object is to provide an improved method for the oxidative conversion of methane. Yet another object is to provide a method for the oxidative conversion of methane at improved conversion levels. Another and further object of the present invention is to provide a method for the oxidative conversion of methane, which results in improved selectivity -to higher hydrocarbons. A further object of the present invention is to provide a method for the oxidative conversion o~ methane, which results in improved conversion and selectivity to higher hydrocarbons. A still further object of the present invention is to provide a method for the oxidative conversion of methane, which results in improved selectivity to ethylene and ethane. Yet another object of the present invention is to provide a methcd for the oxidative conversion of methane, which results in improved conversion and selectivity to ethylene and ethane. Another object of the ~7~3 31754CA
present invention is to provide a method Eor the oxidative conversion of methane, which results in improved selectivity to ethylene. Another and further object of the present invention i8 to provide a method .Eor the oxidative conversion of methane, which results in improved corlversion and selectivity to ethylene. A further object oE the present invention is to provide a method for the oxidative conversion of methane, which can be carried out utiliæing inexpensive starting materials. Another object of the present invention is to provide a method for the oxidative conversion of methane, which can be carried out under relatively mild conditions. A
still further object of the presen-t invention is to provide a method for the oxidative conversion of methane utilizing an improved contact material.
These and other objects and advantages of the present invention will be apparent from the following description.
In accordance with the present invention it has been found that methane can be converted to higher hydrocarbons, particularly ethylene and ethane, by:
contacting a feed material comprising methane with a solid contact material, comprising:
cobalt; at least one metal selected from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth; phosphorous; at least Group IA metal; oxygen, and, optionally, a material selected from the group consisting of a halogen and sulfurj under oxidative conversion conditions sufficient to convert said methane to said higher hydrocarbons.
Substantially improved conversion of methane and selectivity to higher hydrocarbons, particularly ethylene and ethane, is obtained by the addition of a halogen, preferably chlorine.
The method can be carried out in a cyclic manner (methane conversion, preferably followed by a purge with an inert gas, such as nitrogen, and regeneration by contact with a free oxygen containing gas).
However, the further addition of sulfur to the contact material not only increases conversion of methane and selectivity to higher hydrocarbons, particularly ethylene and ethane, but permits the method to be carried out in a continuous manner (by contacting a methane-containing gas and a free oxygen containing gas with the contac-t material).
7~3 3l75l~CA
Zirconium is a preferred metal from the group consisting of æirconium, zinc, niobium, indium, lead and bismuth. The preferred Group IA metal is sodiwm. However, the addition of a second Group I~ metal, preferably potassium, improves results ~Inder certain operating conditions.
Detailed De~ ption In accordance with the present inven-tion~ it has been found that substantially improved conversion of methane to higher hydrocarbons can be obtained by the oxidative conversion of methane to produce higher hydrocarbons at substantially improved selectivities, particularly to ethylene and ethane, by:
contacting a methane-containg gas with a solid contact material, comprising:
cobalt; at least one metal selected from the group consisting of zirconium, ~inc, niobium, indium, lead and bismuth; phosphorous; at least one Group IA metal; oxygen, and, optionally, at least one material selec-ted from the group consisting of a halogen and sulfur, under oxidative conversion conditions suEficient to convert the methane to higher hydrocarbons, particularly ethylene and ethane.
A preferred metal from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth is zirconium. A preferred Group IA
metal is sodium, resulting in the following combination:
Co/Zr/P/Na/0 While the above contact material is capable of converting methane to higher hydrocarbons, particularly ethylene and ethane, the conversion and selectivity are relatively poor. ~lowever, the addition oi a halogen, such as chlorine, to this composition substantially improves both the conversion of methane and the selectivity to higher hydrocarbons, particularly ethylene and ethane. The chlorine can be added to the contact material during its preparation, thus resul-ting in the following contact material:
Co/Zr/P/Na/Cl/0 or by pretreating the contact material with a halogen-containing gas în the reac-tor prior to conduct of -the reaction, as will be detailed hereinafter in the description of the preparation of the contact material and the methods of operation.
~ 3 31754CA
In accordance with most previous theories of the function and operation of contact materials for the oxidative conversion of methane to higher hydrocarbons, particularly ethylene and ethane, the reaction has been carried out in the absence of a Eree o~ygen containing gas, with the oxygen theoretically being supplied by the contact material. As a result, the most utilized modes of operation have included treating the contact material wi-th a free oxygen containing gas, such as oxygen or air, for a period of time sufficient to produce a reducible oxide of a multivalent metal, thereafter, contacting methane wi-th the reducib:le metal oxide and, thereafter, treating the reduced metal oxide with a free oxygen containing gas to "regenerate" the same. Similarly, certain contact materials are contacted with a free oxygen containing gas to cause adsorption of oxygen on the contact material, methane is, thereafter, contacted with the contact material containing adsorbed oxygen and, thereafter, the contact material is again treated with a free oxygen containing gas. In both instances, the contact material, after treatment with a free oxygen containing gas, is purged with an inert gas, such as nitrogen, to remove excess oxygen which has not reacted with or been adsorbed on the contact material. Consequently, several techniques have been followed, including, carrying out the contact with methane and the con-tact wi-th a free oxygen containing gas in separate reaction chambers or sequentially passing a free oxygen containing gas, a purge gas and methane through the contact material in a single reaction vessel.
The disadvantages of either of these procedures will be evident to one skilled in the art.
The method of the present invention can be carried out in a cyclic manner as set for-th above. For example, the methane feed can be passed through a fixed bed of the contact material ~mtil such time as the conversion and/or selectivity reach an unacceptable point. Flow of feed methane is then discontinued and the catalyst is purged with an inert gas, such as nitrogen. Following this purge, a free oxygen containing gas, such as air, is passed therethrough to regenerate the contact material. This cycle is then repeated. Some of the problems with such a cyclic operation are pointed out above and these and others are well known to those skilled in the art.
3~754C~
It has been Eound that the me-thod can be carried out in an essentially continuous manner while at the same time further increasing both the conversion of methane and the selectivity to higher hydrocarbons, particularly ethylene and ethane, by the further addition of sulfur to the contact material. This will result in the following contact material:
Co/Zr/S/P/Na/Cl/0 A brief example of such an operation involves passing a methane-containing gas and a free oxygen containing gas over the above mentioned contact material. When utili~ing this contact material and carrying out the method in an essentially continuous manner, it has been found that the contact material maintains its conversion and selectivity abilities for extended periods of time without further treatment of the contact material or regeneration. However, should such further treatment or regeneration be necessary or desirable, this contact material can also be treated or regenerated periodically as detailed hereinafter.
While -the preferred alkali metal is sodium, as set forth above, it is also desirable to include a second Group IA metal, particularly potassium, thereby resulting in the following contact material:
Co/Zr/S/P/Na/K/Cl/0 The inclusion of potassium in the contact ma-terial has some effect on the conversion of methane and selectivity to higher hydrocarbons but can be eliminated. ~owever, the presence or absence of potassium is significant if a particular method of forming the contact material and operating the process is followed. Specifically, if a halogen, particularly chlorine, is included in the catalyst, which of course is necessary for best results, the presence or absence of potassium is not a significant ~factor. However, if -the contact material is prepared without the halogen, the halogen may be added by pretreating the contact material with a halogen-containing gas, such as methyl chloride, and, thereafter, passing the feed over the contact material for the reaction. In -this case, the presence or absence of potassium is not too significant.
However, if the contact material is prepared without the halogen and a gas containing halogen is co-fed with the feed material, during the reaction, in an effor-t to supply the halogen, then the presence of potassium in the contact material appears necessary.
~ 7~3 31754CA
In addition to methane, the hydrocarbon Eeedstock, employed in the me~hod o-f the present invention, may contain other hydrocarbon or non-hydrocarbon components. The presence of ethane, propane and the like is not detrimen-tal. It has been found that carbon dioxide and water are not detrimen-tal, since they are often products of the process. It has also been found that inert gases, such as nitrogen, helium and the like are not detrimental. Consequently, the method of the present invention can effectively utilize any conventional na-tural gas.
The free oxygen containing gas may be any sui-table oxygen containing gas, such as oxygen, oxygen-enriched air or air. The method of the present application has been effec-tively carried out utilizing air as a source of oxygen.
When utilized in -the present invention, the term "diluent gas"
is meant to include any gaseous material, present in the methane-containing gas, the free oxygen containing gas or in the form of an added gas, which is essentially inert with respect to the oxidative conversion of methane and, thus, does not significantly decrease the conversion of methane and/or the selectivity to the production of higher hydrocarbons.
As previously pointed out, cer-tain of the components of the contact material are an absolute necessity (cobalt, a metal selected from the ~roup consisting of zirconium, æinc, niobium, indium, lead and bismuth, phosphorous, at least one Group IA metal and oxygen). A halogen is necessary in order to attain acceptable conversion and selectivity.
T~e sulfur is necessary to permit essentially continuous operation o-f the method. A second Group IA metal, such ~s potassium, is desirable.
However, the rela~ive proportions of the components does not appear to be particularly critical. Accordingly, any amounts of the individual components may be present so long as effective amounts of the other components are present. The term "effective amount" is used herein to identify the quantity of the component which, when present in the contact material, results in a significant inerease in the conversion of methane and/or the selectivity to higher hydrocarbons, particularly ethylene and ethane, compared with a contact material without the component in question. Preferably, however, the cobalt and the metal selected from the group consisting of zirconium, zinc, niobium, indium, lead and 3175~1C~
bismuth are utilized as major components whi:Le tke remaining components are utilized in minor amounts. By way of example, the preferable atorllic ratio of cobalt to the metal selected Erom the group consisting of zirconium, zinc, niobium, indium, lead and bismuth is in the range of about 1/1 to about 20/1 and more preferably in the range of abou-t 3/1 to about 6/l. The phosphorous is preferably present in an amount of about 1 w-t. percent to about 10 wt. percent and more preferably between about 2 wt. percent and about 5 wt. percen-t, expressed in terms of phosphorous oxide based on the total weight of the contact material. Preferably, the alkali metal is present in concentrations of about 1 wt. percent to about 10 wt. percent and more preferably between about 2 wt. percent and about 5 wt. percent, also expressed in terms of alkali metal oxide based on the total weight of the contact material. Preferred concentrations of sulfur are in the range of about 1 wt. percent to about 10 wt. percent and more preferably between about 2 wt. percent and about 5 wt. percent, expressed in terms of elemental sulfur based on the total weight of -the contact material. The halogen is preferably present in an amount between about 1 wt. percent and about 10 wt. percent and more preferably between about 2 wt. percent and about 5 wt. percent, expressed in terms of elemental halogen based on the total weight of the contact material.
In addition to the appropriate composition, the method of preparation of the contact material is a critical factor in order to obtain an acceptable catalyst, i.e., active, selective and relatively long lived. While it is not intended to restrict the presen-t invention to any particular ~orm of the components or mode of operation in the reaction, it is believed that the contact material is a complex mixture of oxides of the elements contained therein, with the possible e~ception that sulfur and chlorine, which may be present in sulfides or chlorides, thus reducing the amount of oxygen needed to stoichiometrically balance the remainder of the components therein. Theoretically, it is also believed that the components should be in their lower states of oxidation and that some minimal concentration of halogen is necessary.
The contact materials can be prepared by any suitable me-thod known in the art for the preparation of such mixtures in a solid form.
Conventional methods include co-precipitation from an aqueous, an organic or a combination solution-dispersions, impregnation, dry mixing, wet ~ ~r~ 3 31754CA
''` 10 mixing or the like, alone or in various combinations. In general any method can be used which provides contact materials containing the prescribed components in eE~ective amounts. The contact material can be prepared by mixing the ingredients in a blender with enough water to form a thick slurry. The slurry can then be dried, usually the temperat-lre sufficient to volatalize the water or other carrier, such as about 220F
to about 450F and, thereafter, calcined, for example, at about 700F to about 1200F for from 1 to 24 hours. It is believed that the drying step, previously mentioned, results in at least some of -the components being in a higher state of oxidation and, therefore, resulting in an unacceptable contact material. Consequently, it is believed that the components must be reduced -to lower states of oxidation to produce an acceptable contact material. This can be accomplished in several ways.
In accordance with one mode of operation, the contact material is calcined in an oxygen ree atmosphere, for example, in the presence of an inert gas, such as ni-trogen, or a reducing gas, such as hydrogen, methane, ethane, etc. The mode of contacting with the oxygen free atmosphere is also believed significant. For example, it has been found that calcining the contact ma-terial in an open dish while blowing nitrogen through the furnace results in an unacceptable contact material.
On the other hand, when the contact material was calcined in a closed container with nitrogen moving through the solid mass, an acceptable catalyst was obtained. Obviously, the contact material could be calcined in a vacuum but this is impractical. As an alternative, the simpler procedure of calcining in air can be carried out and the contact material placed in the reactor and pretreated with a reducing gas, such as the methane feed, in the absence of oxygen. ~ollowing the pretreatment, the methane eed and oxygen are passed through the reactor to carry out the reaction. The contact material can also be initially prepared without the halogen and, therea~ter, the halogen can be supplied by pretreating the contact material in the reactor with a halogen-containing gas such as methyl chloride, me-thylene chloride, etc. Obviously, if the contact material is prepared by calcining in air and without halogen, the pretreatment would co~prise treatment wi-th a halogen containing gas and a reducing gas in either sequence or in combination. While work to date has not shown any significant deactivation of the contact material during ~ 3 3l754CA
the reaction, either with respect to the conversion oE methane or the selectivity to higher hydrocarbons, it may, from time to time, be necessary to regenerate -the contact material. As previously pointed out, a certain minimal level of chlorine on or near the surface of the contact material appears necessary and it also appears that the contact material should be in a lower state of oxidation. During use for some purposes, it has been found that the contact material deteriorates to some exten-t by loss of chlorine and overoxidation. To the extent that these phenomena occur, it has been found that the contact material may be reactivated or regenerated by stopping the flow of feed methane and free oxygen containing gas, passing a halogen containing gas through the contact material and, thereafter, passing a reducing gas, such as the feed methane alone, through the contact material. This treatment returns the activity and selectivity of the contact material to essentially its original condition.
Any suitable cobalt compound may be utilized in preparation of the contact material. For example, such compounds would include cobalt acetate, cobalt carbonate, cobalt nitrate, cobalt oxides and cobalt halides. Preferably, the cobalt is present in the preparation material as cobalt sulfide. However, other sulfur compounds may be used such as zirconium, cobalt, sodium, potassium, ammonium sal-ts of sulfur, thiocyanide or thiosulfate.
Any suitable compounds of the metal selected from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth may also be utili~ed in the preparation. Zinc compounds could include zinc acetate, zinc halides, zinc nitrate, zinc carbonate and zinc oxide.
Titanium compounds can include titanium tetrachloride and titanium dioxide. Suitable zirconium compounds include zirconium tetrachloride, zirconyl nitrate, zirconyl acetate and zirconium dioxide. Niobium compounds include niobium chloride and niobium oxide. Suitable indium compounds can be utilized, such as indium chloride, indium hydroxideS
indium nitrate, indium acetate and indium oxide. Lead compounds which may be utilized include lead chloride, lead nitrate, lead acetate, lead carbonate and lead oxides. Bismuth may be in the form of bismuth trichloride, bismuth nitrate, bismuth subnitrate and bismu-th trioxide.
~ 3 3175~CA
lZ
The alkali metal and phosphorous are preferably added to the preparation composition as sodium dihydrogenorthophosphate, disodiummonohydrogenorthophosphate, trisodiumorthophosphate and sodiumpyrophosphate. The alkali metal and phosphorous can be incorporated separately, utilizing sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium nitrate and sodium acetate and ammonium hydrogen phosphates. As previously indicated, it is believed that -the contact material is a complex mixture of oxides.
Consequently, it is preferred that -the starting materials be in -their oxide form or in -the form of compounds which, upon drying and/or calcining, are converted to oxides.
In the present invention, it has been found -that the method can be carried out between two extremes, namely, low conversion of methane/high selectivity to higher hydrocarbons, particularly ethylene, and high conversion of methane/low selectivity to the higher carbons, particularly ethylene. The process parameters (space velocity, temperature, and reactant partial pressure) can, to some extent, be used to control the reaction at the desired point between these two limits.
Consequently, the reaction conditions may vary between broad limits.
The vol~etric ratio of methane to free oxygen should be in excess of about 1/1, preferably it is between about 1/1 and about 30/1 and still more preferably between about 4/1 and about 15/1. It has been found that a ratio of methane to free oxygen of at least about 1/1 is necessary, in accordance with the present invention, in order to obtain maximum conversion of methane and high selectivity to higher hydrocarbons, particularly ethylene.
The temperature is preferably at least about 500C and will generally vary between about 500C and about 1500C. However, in order to obtain high conversions of methane and high selectivities to ethylene and ethane, the temperature is preferably between about 500C and about 900C and most desirably between about 600C and about 800C.
It has also been found that, as the partial pressure of oxygen is increased, the selectivity to higher hydrocarbons decreases and the selectivity to carbon dioxide increases and vice versa. Total pressures may vary anywhere from around 1 atmosphere to about 1500 psi but are preferably below about 300 psi and ideally below abou-t 100 psi.
~ 31754C~
nethane f]ow rates can also vary over a wide range, for example, from 0.5 to 100 cubic centimeters per mi.nute per cubic centimeter of contact ma-terial. Preferably, however, the rate is between about 1.0 and about 75 c-Lbic centimeters per minute per cubic centimeter of contact material.
The total flow velocities of all gaseous materials, including diluents, through a fixed bed reactor, may be at any rate effective for the oxidative conversion reaction. For example from 50 to 10,000 GHSV
and preferably from 500 to 5000 GHSV.
In addition to the high conversion oE methane and high selectivity to ethylene and ethane, attainable in accordance with the present invention, the contact materials are not readily poisoned and will tolerate the presence of water, carbon dioxide, carbon monoxide and the like. In addition, the contact materials appear to be long lived, with no noticeable deactivation problems. Concomitantly, the process can be carried out sontinuously in fixed, moving, fluidized, ebullating or entrained bed reactors.
The following examples illustrate the nature and advantages of the present invention.
In the runs of the examples, the contact materials were prepared by aqueous slurrying, drying and calcination.
The contact material was loaded in a quartz reactor having a thermocouple well centered in the contact material bed. The reactor was brought up to temperature under ni-trogen or air and, thereafter, methane and air flow was begun. The gas inlet system included electronic flow measurement, a three-~one furnace for heating reactant gases and the contact material and a downstream analysis system. The reactor effl~ent was snap sampled, at any desired time, and analyzed for all paraffins and olefins between Cl and C4 and N2, 2, C0 and C02, by gas chromatography.
All contact materials are referred to in terms of weight percent of the designated element, based on the total weight of contact material.
The variables and results of this series of tests are set forth in the Table below. Conversion is mole percent of methane converted.
Selectivity and yields are based on mole percen-t of methane feed converted to a particular product. The CH~ rate can be expressed as cc/min/cc of contact material. ~or example, when 70 cc/min of CH~ was ~ 7~3 31754CA
fed to a reactor containing 20 cc of catalyst the flow ra-te would be 3.5 cc/min of CH~/cc of contact material. The volumetric ratio of CH4 to oxygen is also parenthetically given in terms of cc/min of Cll~ per cc/min of other gases (air) present. The Co/Zr/S/P/Na/K/Cl/0 contact mater:ial was prepared by the following procedure: 107.1 g of CoCl2 was dissolved in 250 m~ of distilled water and 118.9 g of Na2S was dissolved in 250 ml of water. These two solutions were combined and stirred for about 20 minutes, filtered, using a Buchner funnel, the precipitate was washed in distilled water and refiltered. An aqueous slurry of the resultant CoS
was formed with Na4P207 10H20(7.5g)Na, X0~1(1.5g), ~rO(N03)2 nH20(26.7g) and NH4C1(5.4g). The slurry was then dried over night in a forced draft oven. The dried contact ma-terial was calcined in a quartz calcining reactor for three hours at 1500F in a flowing nitrogen atmosphere. The calcined contact material was then ground and sieved to 20/40 mesh.
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- l6 It has also been found that the production of CO2 was high and, hence, the HC selectivi-ty was low, if the concentration o~ 2 in the initial feed stream is high. Accordingly, the ~IC selectivity can be increased and the CO2 production concom:ittantly decreased by staged addition oE the free oxygen containing gas to provide an effective portion of the total 2 at a plurality of spaced points along a continuous contact material bed or between separate con-tact material beds.
While specific materials, conditions of operation, modes of operation and equipment have been reierred to herein, it is to be recognized that these and other specific recitals are for illustrative purposes and to set forth the best mode only and are not to be considered limiting.
Claims (16)
1. A method for the oxidative conversion of methane to higher hydrocarbons, comprising:
contacting a feed material comprising methane with a solid contact material, comprising:
cobalt; at least metal selected from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth; phosphorous; at least Group IA metal; oxygen, and, optionally, at least one material selected from the group consisting of a halogen and sulfur, under oxidative conversion conditions sufficient to convert said methane to said higher hydrocarbons.
contacting a feed material comprising methane with a solid contact material, comprising:
cobalt; at least metal selected from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth; phosphorous; at least Group IA metal; oxygen, and, optionally, at least one material selected from the group consisting of a halogen and sulfur, under oxidative conversion conditions sufficient to convert said methane to said higher hydrocarbons.
2. A method in accordance with claim 1 wherein the feed material is natural gas.
3. A method in accordance with claim 1 wherein the metal selected from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth is zirconium.
4. A method in accordance with claim 1 wherein the Group IA
metal is sodium.
metal is sodium.
5. A method in accordance with claim 1 wherein the contact material is prepared by:
combining compounds of the elements; and calcining the thus combined compounds in an oxygen free atmosphere.
combining compounds of the elements; and calcining the thus combined compounds in an oxygen free atmosphere.
6. A method in accordance with claim 1 wherein the contact material is prepared by:
combining compounds of the elements; and calcining the thus combined compounds in the presence of a free oxygen containing gas;
placing the thus calcined contact material in a reaction zone;
passing a reducing gas through the contact material in said reaction zone and, thereafter;
passing the feed material through the contact material.
combining compounds of the elements; and calcining the thus combined compounds in the presence of a free oxygen containing gas;
placing the thus calcined contact material in a reaction zone;
passing a reducing gas through the contact material in said reaction zone and, thereafter;
passing the feed material through the contact material.
7. A method in accordance with claim 6 wherein the reducing gas is methane.
8. A method in accordance with claim 1 wherein the contact material contains chlorine.
9. A method in accordance with claim 1 wherein the contact material additionally contains potassium.
10. A method in accordance with claim 1 wherein the contact material contains sulfur.
11. A method in accordance with claim 10 wherein the feed material is contacted with the contact material in the presence of a free oxygen containing gas.
12. A method in accordance with claim 11 wherein the method is carried out in an essentially continuous manner.
13. A method in accordance with claim 11 wherein the volumetric ratio of methane to free oxygen is at least about 1/1.
14. A method in accordance with claim 11 wherein the volumetric ratio of methane to free oxygen is between about 1/1 and about 30/1.
15. A method in accordance with claim 1 wherein the temperature of contacting is at least about 500°C.
16. A method in accordance with claim 1 wherein the temperature of contacting is between about 500°C and 1500°C.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/742,339 US4620057A (en) | 1985-06-07 | 1985-06-07 | Methane conversion |
US742,339 | 1985-06-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1247143A true CA1247143A (en) | 1988-12-20 |
Family
ID=24984440
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000507766A Expired CA1247143A (en) | 1985-06-07 | 1986-04-28 | Methane conversion |
Country Status (12)
Country | Link |
---|---|
US (1) | US4620057A (en) |
EP (1) | EP0205117B1 (en) |
JP (1) | JPH0618790B2 (en) |
CN (1) | CN1006784B (en) |
AT (1) | ATE46140T1 (en) |
AU (1) | AU571141B2 (en) |
CA (1) | CA1247143A (en) |
DE (1) | DE3665448D1 (en) |
MX (1) | MX164849B (en) |
MY (1) | MY101157A (en) |
NO (1) | NO862267L (en) |
NZ (1) | NZ216034A (en) |
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CA1250317A (en) * | 1984-04-16 | 1989-02-21 | C. Andrew Jones | Methane conversion |
US4994598A (en) * | 1985-03-19 | 1991-02-19 | Phillips Petroleum Company | Oxidative conversion of organic compounds |
US4982038A (en) * | 1985-03-19 | 1991-01-01 | Phillips Petroleum Company | Oxidative methylation of organic compounds |
US4925997A (en) * | 1985-03-19 | 1990-05-15 | Phillips Petroleum Company | Oxidative conversion of organic compounds, toluene and acetonitrile |
US5157188A (en) * | 1985-03-19 | 1992-10-20 | Phillips Petroleum Company | Methane conversion |
US4658076A (en) * | 1985-03-19 | 1987-04-14 | Phillips Petroleum Company | Composition of matter and method of oxidative conversion of organic compounds therewith |
US4950836A (en) * | 1985-06-07 | 1990-08-21 | Phillips Petroleum Company | Oxidative methylation of organic compounds |
DE3534530A1 (en) * | 1985-09-27 | 1987-04-09 | Manfred Prof Dr Baerns | Continuous process for the oxidative coupling of methane to C2+ hydrocarbons in the presence of catalysts |
GB8600260D0 (en) * | 1986-01-07 | 1986-02-12 | British Petroleum Co Plc | Chemical process |
JPS62238220A (en) * | 1986-04-05 | 1987-10-19 | Idemitsu Kosan Co Ltd | Production of hydrocarbon |
US5012028A (en) * | 1986-07-11 | 1991-04-30 | The Standard Oil Company | Process for upgrading light hydrocarbons using oxidative coupling and pyrolysis |
US4769507A (en) * | 1987-03-30 | 1988-09-06 | National Distillers And Chemical Corporation | Process for making higher hydrocarbons from methane |
US4886931A (en) * | 1987-06-04 | 1989-12-12 | The Standard Oil Company | Upgrading low molecular weight hydrocarbons |
US4795842A (en) * | 1987-08-04 | 1989-01-03 | Atlantic Richfield Company | Methane conversion process |
US4973786A (en) * | 1987-10-19 | 1990-11-27 | Karra Sankaram B | Process for the pyrolytic oxidation of methane to higher molecular weight hydrocarbons and synthesis gas |
US4864074A (en) * | 1988-05-03 | 1989-09-05 | Mobil Oil Corporation | Process for converting methane to higher molecular weight hydrocarbons via sulfur-containing intermediates |
US4864073A (en) * | 1988-05-03 | 1989-09-05 | Mobil Oil Corporation | Processes for converting methane to higher molecular weight hydrocarbons via sulfur-containing intermediates |
JPH0639403B2 (en) * | 1990-03-31 | 1994-05-25 | 工業技術院長 | Hydrocarbon production method |
GB2252104A (en) * | 1991-01-28 | 1992-07-29 | British Gas Plc | Hydrocarbon conversion |
KR0156272B1 (en) * | 1993-12-31 | 1998-12-01 | 강박광 | Catalyst for conversion of methane to ethylene preparation thereof and process for manufacturing ethylene using said catalyst |
WO2010059529A2 (en) | 2008-11-19 | 2010-05-27 | Merial Limited | Compositions comprising an aryl pyrazole and/or a formamidine, methods and uses thereof |
US8450546B2 (en) * | 2009-06-29 | 2013-05-28 | Fina Technology, Inc. | Process for the oxidative coupling of hydrocarbons |
US8912381B2 (en) * | 2009-06-29 | 2014-12-16 | Fina Technology, Inc. | Process for the oxidative coupling of methane |
BR112014000757A2 (en) * | 2011-07-18 | 2017-02-14 | Univ Northwestern | method to form ethylene |
CA2855954C (en) | 2011-11-17 | 2020-09-01 | Merial Limited | Compositions comprising an aryl pyrazole and a substituted imidazole, methods and uses thereof. |
US10227268B2 (en) * | 2015-02-19 | 2019-03-12 | Northwestern University | Sulfur as a selective oxidant in oxidative hydrocarbon processing over oxide/chalcogenide catalysts |
WO2018148145A1 (en) | 2017-02-07 | 2018-08-16 | Sabic Global Technologies, B.V. | A process for catalytic oxidative dehydrogenation of ethane to ethylene in the presence of chlorine intermediates |
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US1863212A (en) * | 1925-09-17 | 1932-06-14 | Ig Farbenindustrie Ag | Manufacture of liquid hydrocarbons |
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US3845156A (en) * | 1972-04-05 | 1974-10-29 | Phillips Petroleum Co | Processes for dehydrogenation of organic compounds |
US4205194A (en) * | 1978-05-08 | 1980-05-27 | Exxon Research & Engineering Co. | Process for the conversion of relatively low molecular weight hydrocarbons, to higher molecular weight hydrocarbons, catalyst-reagents for such use in such process, and the regeneration thereof |
US4239658A (en) * | 1979-04-05 | 1980-12-16 | Exxon Research & Engineering Co. | Catalysts for the conversion of relatively low molecular weight hydrocarbons to higher molecular weight hydrocarbons and the regeneration of the catalysts |
US4368346A (en) * | 1980-08-26 | 1983-01-11 | Phillips Petroleum Company | Oxidative dehydrogenation of paraffins with a promoted cobalt catalyst |
US4396537A (en) * | 1981-05-01 | 1983-08-02 | Phillips Petroleum Company | Promoted cobalt catalyst |
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NZ203822A (en) * | 1982-04-29 | 1985-04-30 | British Petroleum Co Plc | Process for converting hydrocarbon feedstock to aromatic hydrocarbons |
US4443648A (en) * | 1982-08-30 | 1984-04-17 | Atlantic Richfield Company | Methane conversion |
US4523049A (en) * | 1984-04-16 | 1985-06-11 | Atlantic Richfield Company | Methane conversion process |
US4444984A (en) * | 1982-08-30 | 1984-04-24 | Atlantic Richfield Company | Methane conversion |
US4443645A (en) * | 1982-08-30 | 1984-04-17 | Atlantic Richfield Company | Methane conversion |
US4443646A (en) * | 1982-08-30 | 1984-04-17 | Atlantic Richfield Company | Methane conversion |
US4443649A (en) * | 1982-08-30 | 1984-04-17 | Atlantic Richfield Company | Methane conversion |
US4499322A (en) * | 1983-08-12 | 1985-02-12 | Atlantic Richfield Company | Methane conversion |
US4443644A (en) * | 1982-08-30 | 1984-04-17 | Atlantic Richfield Company | Methane conversion |
DE3237079A1 (en) * | 1982-10-07 | 1984-04-12 | Manfred Prof. Dr. 4630 Bochum Baerns | METHOD FOR THE PRODUCTION OF ETHANE AND OR OR ETHYLENE FROM METHANE |
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US4523050A (en) * | 1984-04-16 | 1985-06-11 | Atlantic Richfield Company | Methane conversion process |
US4544785A (en) * | 1984-04-16 | 1985-10-01 | Atlantic Richfield Company | Methane conversion |
DE3503664A1 (en) * | 1985-02-04 | 1986-08-07 | Akzo Gmbh, 5600 Wuppertal | METHOD FOR THE PRODUCTION OF ETHYLENE-ETHANE MIXTURES |
DE3508571A1 (en) * | 1985-03-11 | 1986-09-11 | Akzo Gmbh, 5600 Wuppertal | METHOD FOR THE PRODUCTION OF ETHYLENE-ETHANE MIXTURES |
US5157188A (en) * | 1985-03-19 | 1992-10-20 | Phillips Petroleum Company | Methane conversion |
-
1985
- 1985-06-07 US US06/742,339 patent/US4620057A/en not_active Expired - Fee Related
-
1986
- 1986-04-28 CA CA000507766A patent/CA1247143A/en not_active Expired
- 1986-04-29 CN CN86102908A patent/CN1006784B/en not_active Expired
- 1986-05-02 NZ NZ216034A patent/NZ216034A/en unknown
- 1986-05-19 AU AU57548/86A patent/AU571141B2/en not_active Ceased
- 1986-05-21 MX MX2569A patent/MX164849B/en unknown
- 1986-06-02 JP JP61125972A patent/JPH0618790B2/en not_active Expired - Lifetime
- 1986-06-05 DE DE8686107683T patent/DE3665448D1/en not_active Expired
- 1986-06-05 EP EP86107683A patent/EP0205117B1/en not_active Expired
- 1986-06-05 AT AT86107683T patent/ATE46140T1/en not_active IP Right Cessation
- 1986-06-06 NO NO862267A patent/NO862267L/en unknown
-
1987
- 1987-03-06 MY MYPI87000246A patent/MY101157A/en unknown
Also Published As
Publication number | Publication date |
---|---|
NO862267D0 (en) | 1986-06-06 |
AU571141B2 (en) | 1988-03-31 |
MY101157A (en) | 1991-07-31 |
JPH0618790B2 (en) | 1994-03-16 |
MX164849B (en) | 1992-09-29 |
AU5754886A (en) | 1986-12-11 |
EP0205117B1 (en) | 1989-09-06 |
JPS61282323A (en) | 1986-12-12 |
ATE46140T1 (en) | 1989-09-15 |
CN1006784B (en) | 1990-02-14 |
NZ216034A (en) | 1989-07-27 |
EP0205117A1 (en) | 1986-12-17 |
NO862267L (en) | 1986-12-08 |
CN86102908A (en) | 1986-12-03 |
US4620057A (en) | 1986-10-28 |
DE3665448D1 (en) | 1989-10-12 |
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